Sulfur containing vat dyestuffs of the anthraquinone series



Patented May 11, l948 UNITED sr r s {PATENT SULFUR.coN'rAmmG-vA'rnYiss'rUrFson OFFICE! THE ANTHRAQUINQNE SERIES MarioScalera, Somerville, N. 3., assign to American Cyanamid Company, NewYork, N-. 3L, a

corporation of Maine No Drawing. Application March23,

- Serial No. 527,345 v 9 Claims. (01. zen-'32s) V g This inventionrelates to new containing sulfur which may be designated as benzanthroneanthraquinone thioxanthenes. It also relates to a process of preparingthem.

The compounds of the present invention contain the following ringsystem:

The productsare made by condensing bzl-benzanthronyl-anthraquinonylsulfides with an alv'at dyestuiis 'undergoes'ring closureto formanadditional five membered. sulfur. containing 'heterocyclic ring. The.generalzbehaviour of the product obtained is consistent with;eithersassumption.

. Other substituted wbenzanthrone anthraquinone thioxanthenes may beprepared by the alkali fusion of. substitutedbz1-benzanthronyl-1'-anthraquinonyl sulfides orthey may be prepared by.direct substitution; in the parent compound,

for' example-by.halogenation.

The substituted bzlebenzanthronyl-1-anthraquinonyl sulfides mentionedabove are'obtainable by the reaction of a substituted bzl halogenbenzanthrone with l-mercapto anthraquinone; ;or by the reaction ofbzl-halogen benzanthrone with a substitutedlx-mercapto anthraquinone; orby thereaction of bal halogen benzanthrone and l-mercapto anthraquinonebothof which bear substituents in other positions.

Substituted bzl halogen benzanthrones 'use able in this process are, forinstance bzl-chloro- 6-methy1 benzanthrone; nitro bzl halogen benkalinecondensing agentfat moderate'elevatedi temperatures. preferably between1100 andy130' C. Ring closure appears totake place to'produce the newcompounds which contain anew heterocyclic six membered ring. Theringsys- T tem has not been. described before and. therefo're, theproducts-of the present invention constitute a new classofheterocycliciderivatives.

Bzl-benzanthronyl sulfides are known 'and have been subjected to alkalifusion. However. these always resulted in a splitting oi. the'bzlsulfurlinkage with the formation of isodibenzanthrones as main products. Ihave found that if the temperature is not permitted to rise above 140 C.ring closure of my sulfides is eftested-without splitting and the newcompounds of the present invention result. It is desirable not tooperate quite so close to the dividing line of temperature andbest're'sults and most reliable operation are obtained when thetemperature is kept between and C.

A number of compounds can be prepared having the ring system describedabove. The simplest is the unsubstituted compound which is obtainedfronr bzl-benzanthronyl-l'-anthraquinonyl sulfide. However, othercompounds may be condensed in a smaller way. For example,6,bz1-benzanthrony1-bis (l-anthraquin-onyl) sulfide will alsoundergo-condensation to give a. benzanthrone anthraquinone trio'xanthenesubstituted by an anthraquinonyl sulfide group. I have not determinedwith. complete certainty whether this anthraquinonyl sulfide group alsozanthrones (obtainable by nitrating bzl halogen benzanthrone innitrobenzene) bz2-hydroxy bzlbromo benzanthrone, as well as thecorresponding methoxy and ethoxy compounds; fi-benzoylamino bzl bromobenzanthrone; 6, bzl dibromo benzanthrone, etc. In the latter case ofthe dihalogen benzanthrone it is possible to brin two molecules oflemercapto anthraq-uinone into reaction to obtain the sulfide of theformula:

which may then be ring closed in alkaline medium to give one of thetypical compounds of myinvention.,

Examples of substituted l-mercapto anthraquinones useable in thisprocess are, for in- ;stance, l-mercapto-4-(and 5-) benzoylaminoanthraquinone; i-mercapto-4-methoxy anthraquinone;4-mercapto-1,1'-dianthrimide; 1,5- dimercapto anthraquinone, etc. Thesesubstituted mercapto anthraq-uinones are obtainable, in general by theaction of sodium sulfide or polysulfide, in alcoholic medium, on. thecorresponding halogen anthraquinones.

Obviously, when substituents are introduced either in the benzanthroneor in the anthra-- quinone residue of the sulfides used. asstarting,

materials for the compounds of inventlom.

the 2 position, in both the benzanthrone and anthraquinone residue, mustbe left-unsubstituted. to permit formation of thethioxanth'ene ring Thesubstituents in the parent thioxanthene compound may also be introducedafter ring,

closure; the positions occupied by the entering substituents have notbeen determined inmost cases. quinone thioxanthene may be chlorinated toa dichloro or a trichloroderivatlve; 'These chlo- For instance, thebenzanthrone anthrarinated derivatives may be in: turn: reactedwithcompounds containing a mobile hydrogemie g; amino anthraqu-inones, toform new and" valuable? substituted am-ino derivatives-ofi the parentcompound.

The unsubstituted benaanthronex-anthraquinone thioxantheneis a darkpowder whichcrystalli'zes from nitrobenzene in: thaform of. thin blackneedles having a greenish tinge. It? is, soluble in concentrated:sulfuric acid toagive; a brown solution which turnsbright green on d1.-lution to 90% u-lturi-c-acim It dyes cotton blue 7 from a violethydrosulfitebatha' If the concentrated sulfuricacidi= solutionaof; thedyestufii istreated with: hydrogen peroxide derivatives such as; forexample persulfuri'c' acid;

or other peracids, a new-dyestuffi-resultsi which contains additional.oxygemand-has the following formula:

This dyestuii dyes cotton blue-green shades of excellent fastness from ablue-green vat. The dyestuif may be purified by precipitation of itssulfate from 85% sulfuric acid and is then obtained in a: crystallineform.

The invention will be described in greater detail in conjunction withthefollowing specific examples, the parts being by weight.

Example 1 10 parts of bzl-benzanthrony'l l'ranthraquinonyl sulfidehaving the formula:

are introduced into a melt of parts of caustic potash and 75 parts ofmethyl alcohol. A smooth yellow slurry results which is gradually heatedto C. and. held at 125-130 C. for several hours;- It gradually turns toa smooth thin black melt and when. the reaction. appears" complete theproduct is drowned 2000:.parts. of water, boiled and filtered. Thefiltration cake is blue- Lblack and is washed with water until the wash-'10,.

If ethyl alcohol is used in; place of methyl alcohol in the causticiusion" the same product is obtained and the caustic potash may bereplaced by caustic soda, but the meltv is less easily handled.

Example 2 67 parts vof the compound prepared in Example 1 aredi'ssolvedin I0001parts'of96% sulfuric acid; The resultingolive slurry is"treated; with 39 parts 5, of ammomumipersul'fate, dissolved" in .700parts oi 96%, sulfuric.,acid, the temperature-being kept between 30 and50" C. by external cooling if necessary. l f.

The resulting sol'utiorr is drowned in water, filtered, andlwaslre'difree' of. acid"; There is obtaineda green presscakauwhfchmay bedispersed to aldyeing paste ordriedto a blackpowder. hey sldt is quatitative;

The, new'profi l'ctis already inia' pure state it ar/the furthenp tifiijd; if d s r by ss lv it in- 20ipartsof' 98%1 'sul'iuricacid; adding 8parts of sulfuric" acid,;ancf filtering; The product;

when freed from sulfuric acid; is" in the form of green; crystals. Itdyes' cottor-r from a bluegray'vatstrong' blueegreerr shades ofi'goodfastness; particularly to light; It corresponds to-the' formulaz V V VwExamplea V, 7

l parts of bzLd-benZanthronylbis (l-anthraquinonyl) -sulfide of theformula:

(which may be obtained in the form of yellow crystals by reacting6,bz1-dibromo benzanthrone with 2 moles of the sodium salt of l-mercaptoanthraquinone in boiling nitrobenzene in the presence of copper oxide)are introduced into.a melt of 100 parts of caustic potash and 65parts ofmethyl alcohol at 100 C. The'meit is refluxed and held at 130-134" C.for several hours until the change from yellow to black is complete.Thereupon, it is poured into 1500 parts of water, 5 parts of sodium.hydrosulfite is added to prevent premature oxidation, and filtered. Theredbrown filtrate is aerated, resulting in precipitation of the dyestuffwhich is recovered by filtration, the cake being washed with hot wateruntil the out-mm is colorless.

A good yield of the dyestufi is obtained which dyes cotton s'late grayfrom a blue vat. If desired it may be still further purified byrecrystallization from boiling nitrobenzene in which it is somewhatsoluble hot and much less soluble cold. When completely pure it isdichroic in nitrobenzene, giving a green-blue color by transmitted lightand red by reflected light. The purified product dyes cotton a brightblue-gray from a blue-black vat and corresponds to the formula:

the dotted line indicating that a ring closure may or may not haveoccurred between the positions shown.

Example 4 50 parts of benzanthrone anthraquinone thi- 75 sand S=o 6oxanthene, prepared as described in Example. 1, are suspended in 500parts or nitrobenzene. One part of iodine and 15 0 parts of sulfurylchlon'de are then added, and the mixture is agitated at -90 C. for aperiod of several hours.

Example 5 70 parts of chlorinated benzanthrone anthraquinonethioxanthene, obtainable as described in 'Example 4, 60 parts of alphaamino anthraquinone, 30 parts of anhydrous soda ash and 0.5 part ofcopper bronze are slurried together in 750 parts of nitrobenzene.

The mixture is refluxed for 15 to 20 hours, allowed to cool, andfiltered. The product is washed with nitrobenzene, then with alcohol,then steam distilled free of adhering solvent. It is filtered from theaqueous suspension, washed and. dried. I

The product may be purified, if desired, by precipitating its sulfatefrom sulfuric acid of 80% strength. [It dyes the fiber violet shadesfrom a yellowish-gray vat. It has the formula:

I claim:

1. Vat dyestufis of the benzathrone anthraquinone thioxanthene seriescontaining the following ring system:

where X is a member of the group consisting of 2. Aben'zanthroneanthraquinone thioxan thene: of the formulay" 3. An oxidizedbenzanthrone anthraquinone thioxanthene having the formula:

4. A method of producing benzanthrone' anthraquinone thioxanthene vatdyestuffs which comprises subjecting a bzl-benzanthrony-l-anthraquinonylsulfide to alkaline fusion at an. elevated temperature not exceeding 140C.

5. A method of preparing 'benzanthrone anthraquinone thioxanthene whichcomprises subjecting a bzl benzanthrony-l 1' anthraquinonyl'sulfide toan alkaline fusion. at an elevated temperature not exceeding 140 C. l

perature between 100 and 130 Cr 25 Number.

MARIO SCALERA.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Name Date- 1',783;659.'-' 1,999,997 2 ;025,546 r2,059, 64?

Perkins Apr. 30,1935 Nawiasky eta1; Dec. 24, 1935 Perkins Nov. 3, 1936Eichholz Jan. 17, 1939 Lulek Aug. 20; 1940 FOREIGN PATENTS Country DateGreat Britain'- Nov. 17, 1938v Number.

Lutt'ringhams eta1.-- Dec. 20,1939

